Polypropylene-polybutylene laminated packaging film with improved tear strength

ABSTRACT

A packaging film composition having an improved tear strength comprising a core, which is preferably polybutylene homopolymer or copolymer or a blend of polybutylene with another compatible polymer, said core being coated on one or both sides with a polypropylene homopolymer or copolymer optionally blended with a minor amount of a high melt index polybutylene.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a multi-layer, thermoplastic heat-sealable filmsuitable for conventional packaging applications.

2. Brief Description of the Prior Art

Oriented polypropylene film has become a useful and widely acceptedpackaging film because of its good moisture barrier, stiffness, highstrength, and good optical properties. However, the tear strength ofpolypropylene films is relatively low and improvement has long beenneeded. Polybutylene films are known to give the strongest tear strengthamong the unsubstituted polyalphaolefins. However, blending polybutyleneinto polypropylene cannot improve the tear strength of polypropylenesignificantly. The tear strength of polypropylene may, however, besignificantly improved by coextruding polybutylene. The processabilityof a polypropylene/polybutylene structure film is rather poor if thepolybutylene is used as a surface layer, due to the sticky nature ofpolybutylene just prepared from the melt. By sandwiching polybutylene asa core layer, the sticky problem is then eliminated. Adding a smallamount of high melt index polybutylene in the polypropylene layersfurther improves the processability and optics of the laminated films.

U.S. Pat. No. 3,972,964 issued to D. J. Doentremont, discloses a coatingcomposition for heat-shrinkable thermoplastic film comprising blends ofpolybutene-1 with ethylene-propylene copolymer to provide abuseresistance with reduced tackiness without compromising the orientabilityof the base film. However, in order to achieve this objectiveDoentremont specifies that the coating composition must have apolybutene-1 constituent in the range of 5%-40% by weight and that it isundesirable to have more than 40% polybutene-1. Such a coatingcomposition, while achieving the objectives of abuse resistance andreduced tackiness, does not impart good heat sealability to the film.

U.S. Defensive Publication No. T-955,009 (R. C. Lansbury and T. G.Heggs, Feb. 1, 1977) addresses the problem of heat sealability directly.Lansbury and Heggs have found that they can improve the sealability ofpolypropylene film by coextruding the polypropylene substrate with acoating composition comprising a blend of 10%-59% (by weight)ethylene-propylene copolymer with 41%-90% (by weight) of a homo-orcopolymer of a C₄ to C₁₀ alpha-olefin to form a multilayer film having apolypropylene core with a thin coating of such composition on one orboth sides.

U.S. Pat. Nos. 4,125,662; 4,275,120; 4,340,060; 4,340,641; 4,339,493;4,339,494; 4,339,495; and 4,339,496 disclose laminated films having apolypropylene core and polybutylene outer layers.

SUMMARY OF THE INVENTION

The present invention is a novel multi-layer film composition having anunexpectedly high tear strength and good processability. The filmcomprises a "core" or substrate of butylene homopolymer or copolymer orblends of two Butene-1 polymer or blends of Butene-1 polymer withpropylene homopolymers and copolymers. This core is coated on one orboth sides with a layer of propylene homopolymer, or copolymer, thecoating forming a "skin" which may comprise from 3% to 30% of the totalthickness of the coated film.

The film may be made by any conventional technique in which a skinlayer, which is substantially polypropylene or an ethylene-propylenecopolymer, may be applied to a core or base layer consistingsubstantially of polybutylene. Any of the known methods of coextrusionor of extrusion coating can be used to make this film.

The film-forming composition, or any component thereof, can be usedunaltered or can be modified with additives for improvement of slip,antiblock or static properties of the finished film.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The coated thermoplastic film of the present invention may be formed byan conventional technique for producing a multi-layered film, forexample: coextrusion, lamination of previously extruded films; extrusioncoating; emulsion coating; and so forth. The preferred method iscoextrusion, but it is not our intention to limit the means ofproduction to any single technique.

Resins useful for the core layers of the present invention include lowmelt index homopolymers of butene-1 and copolymers of ethylene withbutene-1 wherein the ethylene content is between 0.25% and 10% byweight. The outer skin material may be any homopolymer of propylene, ora copolymer of propylene with ethylene or with butene-1, or it maycomprise a blend of propylene homopolymer or copolymer with anycompatible polymeric substance. For most applications it is preferredthat the outer layer be substantially polypropylene.

The outer layer may also be a blend of polypropylene and a high meltindex polybutylene.

The high melt index poly-1-butene referred to herein is a butene-1polymer containing at least about 90%, preferably at least about 95%,and more preferably about 97%, by weight of isotactic portions. Usefulin the present invention are isotactic poly-1-butenes having a lowmolecular weight, e.g. less than about 280,000 as determined by solutionviscosity in "Decalin" (decahydronophthalene). Usable poly-1-buteneshave a density of 0.900-0.925, preferably 0.905-0.920 and especially0.910-0.915. Usable poly-1-butenes have melt indices in the range offrom 10 to 1000, more preferably 20-650, and most preferably 100-500, asdetermined by ASTM D-1238 Condition E, at 190° C. The intrinsicviscosity of the polybutylene may range from about 0.03 to about 0.20preferably from about 0.06 to about 0.11 at 130° C.

The low melt index butene-1 polymers referred to herein aresubstantially polybutene-1 containing at least 95%, preferably 97%, andmost preferably 98% by weight of isotactic portions. Suitablepolybutenes have a density of 0.914-0.919 and a melt index of less than20 g/10 min. at 190° C.

Suitable polybutenes can be obtained, for example, according toZiegler-Natta low pressure polymerization of butene-1 ad disclosed inGerman Published Application No. 1,570,353.

The butene-1 polymers (PB) usable herein are either butene-1homopolymers or copolymers. If butene-1 copolymers are used, thenon-butene comonomer content is preferably 1-30 mole% of eitherethylene, propylene, or an alpha olefin having from 5 to 8 carbon atoms.

Suitable poly-1-butenes can be obtained, for example, in accordance withZiegler-Natta low-pressure polymerization of butene-1, e.g. bypolymerizing butene-1 with catalysts of TiCl₃ or TiCl₃.AlCl₃ and Al(C₂H₅)₂ Cl at temperatures of 10°-50° C., preferably 20°-40° C., e.g.according to the process of German Published Application No. 1,570,353.High melt indices are then obtained by further processing the polymer byperoxide cracking. The polybutylene may be modified to increase surfaceactivity by reaction with, for example, maleic anhydride or otherfunctional group.

The polypropylene used in the present invention is any crystallizablepolypropylene. Said polypropylene can be prepared by homopolymerizingpropylene irrespective of the method used so long as crystallizablepolypropylene is formed. The preferred polypropylenes are thesubstantially isotactic polypropylenes prepared by the Ziegler/Natta orMgCl₂ -supported catalyst polymerization process.

The propylene polymers usable herein can be either propylenehomopolymers or copolymers. If propylene copolymers are used, they canbe random or block copolymers with the comomoner content preferably 1-30mole % of either ethylene, butene, or an alpha olefin having from 5 to 8carbon atoms.

Propylene polymers useful in the invention preferably have a melt indexof less than 60, more preferably from about 1-15, as measured by ASTMD-1238, Condition L at 230° C. A particularly suitable propylene, has amelt index of 2.6 and is available from Shell Chemical Company, ofHouston, Tex. as PP5AO8.

The laminate compositions may also contain additives and fillers, e.g.mold release agents, UV or thermal stabilizers, slip agents, antiblockagents, nucleating agents, pigments, antioxidants, or flame retardants.

Blending of the components can occur by one of several methods, drytumble blending, masterbatch, or melt compounding techniques. The methodof combining the ingredients of the formulation is important. Forexample, in most cases, it is desirable to use the least amount ofenergy to merge the components into an effective blend. Therefore, thepreferred method of blending is dry blending the components in a powderform.

The skin layer of the laminate structure embodied herein is usually 0.1mil to 0.8 mil for every mil of total film thickness. Generallypreferred is a skin of 0.3 mil to 0.6 mil and a total film thickness of0.9 mil to 2.0 mils.

EXAMPLES

Films may be prepared having a coating on either one or both sides ofthe core film. Films were prepared by coextruding a core material ofpolybutylene copolymer with a coating on both sides thereof comprisingpropylene homopolymer. The molten polymers were coextruded from aconventional extruder through a flat sheet die, the melt streams beingcombined in an adaptor prior to being extruded from the die. Each skinlayer comprised approximately 1/3 of the total thickness of the film.The resin was extruded at about 204° C. (400° F.) for the skin materialand 218° C. (425° F.) for the core material.

After leaving the die orifice, the coated films were quenched in a waterbath at about 10° C. (50° F.). The quenched sheet was then reheated toabout 93° C. (200° F.) and stretched 5X in the machine direction (MD)and subsequently about 7.5X in the transverse direction (TD). The highedges were trimmed off and the film wound on cores.

Using this same basic procedure, films were prepared having thefollowing composition:

Film 1. PP5AO8 polypropylene, single layer, 1.5 mils

Film 2. PP5AO8/PB8640 polybutylene/PP5AO8, 0.5 mil/0.5/mil/0.5 mil

Film 3. PP5AO8/PB8640 (50%)+PB8310 polybutylene (50%)/PP5AO8, 0.5mil/0.5 mil/0.5 mil

Film 4. PP5AO8+PBO800 polybutylene (5%)/PB8640 (50%)+PB8310(50%)/PP5AO8+PBO800 (5%) 0.5 mil/0.5 mil/0.5 mil

The various materials used for the example films were as follows:

PP5AO8 is a polypropylene homopolymer with a melt index of 2.8 g/10 min.at 230° C. density of 0.90, available from Shell Chemical Company,Houston, Tex.

PB8640 is a polybutylene copolymer with an ethylene comonomer content of0.75% by weight, a melt index of 1.0 g/10 min. at 190° C. and amolecular weight of about 550,000, available from Shell ChemicalCompany, Houston, Tex.

PB8310 is a polybutylene copolymer with an ethylene comonomer content of5.5% by weight, a melt index of 4.0 g/10 min. at 190° C., and amolecular weight of about 400,000, available from Shell ChemicalCompany, Houston, Tex.

DPO800 is a polybutylene homopolymer with a melt index of 200 g/10 min.at 190° C., molecular weight of 108,000, available from Shell ChemicalCompany, Houston, Tex.

The typical physical properties of the high melt index polybutylene(DPO800) are listed below.

                                      TABLE I                                     __________________________________________________________________________    Typical Physical Properties of DP0800 Polybutylene                                         ASTM   Unit       Polybutylene                                                Test Method                                                                          English                                                                            (Metric)                                                                            DP0800                                         __________________________________________________________________________    Melt Index                                                                    @ 190° C.                                                                           D1238 "E"                                                                            --   g/10 min                                                                            200                                            @ 210° C.                                                                           D1238 "L"                                                                            --   g/10 min                                                                            490                                            Density      D1505  lb/ft                                                                              g/cm.sup.3                                                                          57.1(0.915)                                    Tensile strength @ yield                                                                   D638   psi  MPa   2000(13.8)                                     Tensile strength @ break                                                                   D638   psi  MPa   4200(29.0)                                     Elongation at break                                                                        D638   %    %     350                                            Modulus of elasticity                                                                      D638   psi  MPa   35000(241)                                     Hardness, Shore                                                                            D2240  D scale                                                                            D scale                                                                             55(55)                                         Brittleness temperature                                                                    D746   °F.                                                                         °C.                                                                          0°(18°)                          Melting point range                                                                        DSC    °F.                                                                         °C.                                                                          255-259°                                                               (124-126°)                              Soft point, Vicat                                                                          D1525  °F.                                                                         °C.                                                                          241°(116°)                       Thermal conductivity,                                                                      C177   Btu/ft.sup.2 /                                                                     Kcal/m.sup.2                                                                        1.25                                           at 77° F.    hr/°F./in                                                                   hr/°C./cm                                                                    (16)                                           __________________________________________________________________________

Table II shows the tear strength improvement obtained by laminatingpolybutylene or a polybutylene blend between polypropylene layer inFilms 2 and 3. Also, Film 4 demonstrates that a small amount of highmelt index polybutylene improves the optical properties while providinghigh tear strength and improved processability. Films having apolybutylene core and those containing a minor amount of high melt indexpolybutylene blended with polypropylene were processed very easily andhad no handling problem since the surface was not tacky.

                  TABLE II                                                        ______________________________________                                        Tear Strength Improvement of Polypropylene Film                               Film Thickness: 38 microns                                                                Sample I.D.                                                                   1     2         3       4                                         ______________________________________                                        Haze, %       9.7     12.2      11.7  11.2                                    Clarity, %    17.7    15.5      15.9  16.2                                    Gloss (60°)                                                                          78.7    76.4      75.3  78.7                                    Tear Strength, G/Mil                                                          MD            8.3     30        48    23                                      TD            211     788       653   866                                     ______________________________________                                    

As can be seen from this data, the laminated films of the presentinvention, i.e. Films 2, 3, and 4 have a significantly higher tearstrength than polypropylene alone (Film 1) while retaining the goodoptical properties and do not have problems associated with a tackysurface.

In addition, Film 4 which contained 5% by weight of a high melt indexpolybutylene in the outer layers, processed more easily with a lowerback pressure and higher throughput rate.

What is claimed is:
 1. A multiple-layer, heat-sealable laminated filmcomprising:(a) a core layer formed from a member of the group consistingof butene-1 homopolymers and copolymers of butene-1 with ethylenewherein the ethylene content is 0.25% to 15% by weight; and (b) on bothsides of said core, an outer layer which comprises about 90% by weightto about 99% by weight of a homopolymer or copolymer of propylene andabout 1% by weight to about 10% by weight of a high melt index,isotactic polybutylene with a melt index in the range of from about 100to about
 1000. 2. The laminated film of claim 1 wherein said high meltindex polybutylene has a melt index in the range of about 150 to about225.
 3. The laminated film of claim 1 wherein said high melt indexpolybutylene is selected from the group consisting of: butene-1homopolymers and butene-1 copolymers having 1-30 mole% of an alphaolefin having from 2-8 carbon atoms.
 4. The laminated film of claim 1,wherein said propylene homopolymer or copolymer is selected from thegroup consisting of: propylene homopolymers and propylene copolymershaving 1-30 mole% of an alpha olefin having from 2-8 carbon atoms. 5.The laminated film of claim 1, wherein said outer layer comprises about93% to about 97% by weight of said propylene polymer and about 3% toabout 7% by weight of said high melt index polybutylene.
 6. Thelaminated film of claim 1 wherein said outer layer is from about 0.3mils to about 0.6 mils thick and the total film thickness is between 0.9and 2.0 mils.
 7. The laminated film of claim 1 wherein the film isoriented by stretching in two directions substantially at right anglesto each other.
 8. The laminated film of claim 1 wherein the film isformed by coextrusion.